WO2015137194A1

WO2015137194A1 - Mononuclear ruthenium complex and organic synthesis reaction using same

Info

Publication number: WO2015137194A1
Application number: PCT/JP2015/056200
Authority: WO
Inventors: 永島　英夫; 祐輔砂田; 元大串; 晃司作田
Original assignee: 国立大学法人九州大学; 信越化学工業株式会社
Priority date: 2014-03-10
Filing date: 2015-03-03
Publication date: 2015-09-17
Also published as: CN106103460A; EP3118205B1; US9884316B2; KR102410256B1; CN106103460B; JPWO2015137194A1; US20170056872A1; EP3118205A4; KR20160133488A; EP3118205A1; JP6241966B2

Abstract

　A neutral or cationic mononuclear ruthenium divalent complex represented by formula (1) can actualize exceptional catalytic activity in at least one reaction among a hydrosilylation reaction, hydrogenation reaction, and carbonyl compound reduction reaction. (In the formula, R¹-R⁶ each independently represent a hydrogen atom or an alkyl group, aryl group, aralkyl group, organooxy group, monoorganoamino group, diorganoamino group, monoorganophosphino group, diorganophosphino group, monoorganosilyl group, diorganosilyl group, triorganosilyl group, or organothio group optionally substituted by X; at least one pair comprising any of R¹-R³ and any of R⁴-R⁶ together represents a crosslinkable substituent; X represents a halogen atom, organooxy group, monoorganoamino group, diorganoamino group, or organothio group; L each independently represent a two-electron ligand other than CO and thiourea ligands; two L may bond to each other; and m represents an integer of 3 or 4.)

Description

Mononuclear ruthenium complex and organic synthesis reaction using it

The present invention relates to a mononuclear ruthenium complex having a ruthenium-silicon bond. More specifically, the present invention has catalytic activity in at least one of industrially useful hydrosilylation reaction, hydrogenation reaction, and reduction reaction of a carbonyl compound. It relates to a mononuclear ruthenium complex.

Hydrosilylation reaction, in which a Si-H functional compound is added to a compound having a carbon-carbon double bond or triple bond, is a useful means for synthesizing organosilicon compounds, and is also an industrially important synthesis. It is a reaction.
As catalysts for this hydrosilylation reaction, Pt, Pd, and Rh compounds are known. Among them, the most frequently used are Pt compounds represented by Speier catalyst and Karstedt catalyst.

A problem of the reaction using a Pt compound as a catalyst is that, when a Si—H functional compound is added to a terminal olefin, a side reaction occurs in which the olefin undergoes internal rearrangement. In this system, there is no addition reactivity with internal olefins, and unreacted olefins remain in the addition product. Excess olefin must be used.
There is also a problem that the selectivity of the α adduct and the β adduct is inferior depending on the type of olefin.

The biggest problem is that the central metals Pt, Pd, and Rh are all extremely expensive noble metal elements, and a metal compound catalyst that can be used at a lower cost is desired. It is being advanced. In particular, although Ru belongs to a noble metal, it is a metal that can be obtained at a relatively low cost, so that a function as a substitute for Pt, Pd, and Rh is required.

As for this Ru compound, a compound having an η ⁶ -arene group and having an organopolysiloxane bonded to a central metal Ru or a vinylsiloxane coordinated has been reported (Patent Document 1). Although this compound has been shown to be effective for the addition reaction of methylhydrogenpolysiloxane and methylvinylpolysiloxane, the yield is low in the reaction at 120 ° C, and 160 ° C in order to obtain a high yield. The reaction must be carried out at high temperatures.
In addition, in Patent Document 1, many patents relating to Ru catalysts are cited as prior documents (Patent Documents 2 to 6). I can't say that.

On the other hand, the hydrogenation reaction of olefins is also an industrially important reaction. However, noble metals such as Pt, Pd, and Rh are used in conventional catalysts, and the use of inexpensive ruthenium is desired among the noble metals. For example, there are those using a trinuclear ruthenium complex as shown in Non-Patent Document 1, and further improvements are desired from the viewpoint of reaction temperature, yield and the like.
Non-Patent Document 2 discloses a mononuclear ruthenium complex effective for the hydrogenation reaction of a tetrasubstituted olefin, which is said to have a low reaction yield, but it has a low turnover number and can be used under high pressure conditions. Reaction conditions are required.

As a method of reducing the carbonyl compound, there is a method of using hydrogen in the presence of a hydrogen compound of aluminum or boron or a noble metal catalyst. Among carbonyl compounds, ketones and aldehydes are known to be stable and easy-to-handle hydride reagents and precious metal catalysts for hydrogenation that can proceed under mild conditions. However, carboxylic acid derivatives such as esters and amides are known. For the reduction, a method using a strong reducing agent such as lithium aluminum hydride or borane is mainly used (Non-patent Document 3). However, since these reducing agents are ignitable and water-inhibiting substances, they are difficult to handle. Also, care should be taken when removing the reacted aluminum or boron compound from the target product. In addition, reduction of carboxylic acid derivatives requires high temperature and pressure hydrogen.
Many methods have been reported that use a hydrosilane compound, methyl hydrogen polysiloxane, which is stable in air and easy to handle, as a reducing agent, but the reaction requires the addition of a strong acid or Lewis acid, and an expensive noble metal catalyst. And Recently, relatively inexpensive ruthenium-catalyzed reduction reactions of carbonyl compounds have been reported, some of which have been applied to amide reduction reactions that require harsh conditions in the conventional method. . Specific examples of the ruthenium catalyst include Non-Patent Documents 4 to 7, and a highly active catalyst exhibiting a higher turnover number is desired.

As a mononuclear complex compound having a σ bond between ruthenium and silicon, a bivalent complex having a six-electron ligand (Non-patent Documents 8 and 9), a tetravalent complex having a two-electron ligand (non-patent Documents 10 and 11), tetravalent complexes having a six-electron ligand (Non-Patent Documents 9 and 12), divalent complexes having a thiourea group on silicon (Non-Patent Document 13), two having a halogen on silicon Known are a valence complex (Non-Patent Document 14), an anion complex (Non-Patent Document 15), and a bivalent complex (Non-Patent Documents 15 and 16) having an agotic Si—H ligand as a dielectron ligand Yes.
Also known are bivalent complexes (Non-Patent Documents 16 and 17) that have no σ bond between ruthenium and silicon and have an aggressive Si—H ligand as a two-electron ligand.
Furthermore, as a mononuclear complex compound having isonitrile as a two-electron ligand, a divalent complex having a σ bond between two ruthenium and silicon, CO, and a halogen group on silicon (Non-patent Document 18), 2 Bivalent complex having a σ bond between one ruthenium and silicon and CO (Non-patent Document 19), Bivalent complex having a σ bond between one ruthenium and silicon and CO (Non-patent Document 20), 2 Divalent complex having one σ bond between ruthenium and silicon and a halogen group on silicon (Non-patent Document 21), and divalent complex having only one σ bond between ruthenium and silicon (Non-patent Document 22) In addition, a divalent complex having no σ bond between ruthenium and silicon (Non-patent Document 17) is known.
However, in the above Non-Patent Documents 8 to 22, the ruthenium complexes disclosed therein may have catalytic activity for hydrosilylation reaction, olefin hydrogen reaction, and / or carbonyl compound reduction reaction. It does not suggest any gender.
On the other hand, as a reaction example using a ruthenium complex as a catalyst, an addition reaction between ethylene and dimethylchlorosilane (Non-patent Document 23) has been reported, but its reactivity and selectivity are low.
In addition, an example of an addition reaction of disilane and ethylene (Non-patent Document 24) has been reported, and a disila metallacycle structure as an intermediate has been proposed as an estimated reaction mechanism. However, the complex structure containing a ligand has not been clarified, and no suggestion of suggesting a dimetallacycle structure has been made. Furthermore, the reaction examples reported here are low in reactivity and selectivity, and cannot be said to be complexes exhibiting sufficient catalytic activity. Moreover, the main product by the reaction mechanism is vinyl silane or cyclic silane by dehydrogenation silylation, and only a small amount of adduct is present.

Japanese Patent No. 5032561 US Patent Application Publication No. 2004/0092759 US Pat. No. 5,559,264 European Patent Application Publication No. 0403706 US Pat. No. 5,248,802 West German Patent Application No. 2810032

The present invention has been made in view of such circumstances, and is capable of exhibiting excellent catalytic activity in at least one of the three reactions of hydrosilylation reaction, hydrogenation reaction, and reduction reaction of carbonyl compound. An object is to provide a mononuclear ruthenium complex having a silicon bond, and a method for performing each reaction under mild conditions using this complex.

As a result of intensive studies to achieve the above object, the present inventors have found that a predetermined neutral or cationic mononuclear ruthenium divalent complex having a ruthenium-silicon bond has been converted into a hydrosilylation reaction, a hydrogenation reaction, and a carbonyl compound. The present inventors have found that the catalyst activity can be exhibited in at least one of the reduction reactions, and that each reaction proceeds under mild conditions, thereby completing the present invention.

That is, the present invention
1. A neutral or cationic mononuclear ruthenium divalent complex represented by the formula (1):

(Wherein R ¹ to R ⁶ are independently of each other a hydrogen atom, X may be substituted with alkyl group, aryl group, aralkyl group, organooxy group, monoorganoamino group, diorganoamino group. Represents a monoorganophosphino group, a diorganophosphino group, a monoorganosilyl group, a diorganosilyl group, a triorganosilyl group, or an organothio group, or any of R ¹ to R ³ and any of R ⁴ to R ⁶ X represents a halogen atom, an organooxy group, a monoorganoamino group, a diorganoamino group, or an organothio group, and L represents a CO atom independently of each other. And represents a two-electron ligand other than a thiourea ligand, and two L may be bonded to each other, and m represents an integer of 3 or 4.)
2. L is molecular hydrogen, amine, imine, nitrogen-containing heterocycle, phosphine, phosphite, arsine, alcohol, thiol, ether, sulfide, nitrile, isonitrile, aldehyde, ketone, alkene having 2 to 30 carbon atoms, carbon number 1 neutral or cationic mononuclear ruthenium divalent complex which is at least one dielectron ligand selected from 2 to 30 alkynes and triorganohydrosilane,
3. 1 neutral or cationic mononuclear ruthenium divalent complex represented by the formula (2),

(Wherein R ¹ to R ⁶ represent the same meaning as described above. L ¹ represents at least one two-electron coordination selected from isonitrile, amine, imine, nitrogen-containing heterocycle, phosphine, phosphite, and sulfide. When a plurality of L ¹ are present, two L ¹ may be bonded to each other, and L ² represents CO, a thiourea ligand, and a two-electron ligand other than L ^1. In the case where a plurality of L ² are present, two L ² may be bonded to each other, m ¹ represents an integer of 1 to 4, m ² represents an integer of 0 to 3, and m ¹ + m ² Satisfies 3 or 4.)
4). L ¹ represents at least one dielectron ligand selected from isonitrile, nitrogen-containing heterocycle and phosphite (provided that when a plurality of L ¹ are present, two L ¹ are bonded to each other). 3) neutral or cationic mononuclear ruthenium divalent complexes,
5. 3 or 4 neutral or cationic mononuclear ruthenium divalent complex wherein L ² is triorganohydrosilane (provided that when two or more L ² are present, two L ² may be bonded to each other) ,
6). The neutral or cationic mononuclear ruthenium divalent complex of any one of 3 to 5 wherein both m ¹ and m ² are 2,
7). R ¹ to R ⁶ are each independently an alkyl group, an aryl group or an aralkyl group (X represents the same meaning as described above), which may be substituted with X, and L ² represents , H—SiR ⁷ R ⁸ R ⁹ and H—SiR ¹⁰ R ¹¹ R ¹² (wherein R ⁷ to R ¹² are each independently an alkyl group, aryl group or aralkyl, optionally substituted with X) X represents the same meaning as described above), and is represented by any one of R ¹ to R ³ and at least one of R ⁴ to R ⁶ or R ⁷ to R. ^At least one set of any one of ⁹ or any of R ¹⁰ to R ¹² and at least one set of any of R ⁴ to R ⁶ or at least one set of any of R ⁷ to R ⁹ Together, they may form a crosslinking substituent, and R ¹ to R ³ Any one of R ⁴ to R ⁶ or at least one set of any of R ⁷ to R ⁹ together forms a bridging substituent, and any of R ¹⁰ to R ¹² And at least one set of any of R ⁴ to R ⁶ and at least one set of any of R ⁷ to R ⁹ may be combined to form a bridging substituent. Nuclear ruthenium divalent complex,
8). The neutral or cationic mononuclear ruthenium according to any one of 1 to 7, wherein any one of R ¹ to R ³ and any one of R ⁴ to R ⁶ are combined to form a bridging substituent. Divalent complexes,
9. Any one of R ¹ to R ³ and any one of R ⁴ to R ⁶ or any one of R ⁷ to R ⁹ together form a bridging substituent, and R ¹⁰ to Any one of R ¹² and any one of R ⁴ to R ⁶ and any one of R ⁷ to R ⁹ together with a substituent on Si that is not involved in the formation of the bridging substituent; 7 neutral or cationic mononuclear ruthenium divalent complexes forming a cross-linking substituent,
10. Any one of R ¹ to R ³ and any one of R ⁴ to R ⁶ together form an o-phenylene group which may be substituted with Y (Y is a hydrogen atom, a halogen atom, An atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and when there are a plurality of Y, they may be the same or different from each other), and any of R ¹⁰ to R ¹² ⁹ and any one of R ⁷ to R ⁹ together form an o-phenylene group (Y represents the same meaning as above) optionally substituted with Y. Or cationic mononuclear ruthenium divalent complex,
11. A catalyst having activity in at least one reaction selected from a hydrosilylation reaction comprising a neutral or cationic mononuclear ruthenium divalent complex of any one of 1 to 10, a hydrogenation reaction, and a reduction reaction of a carbonyl compound;
12 A process for producing an addition compound comprising hydrosilylation reaction of a compound having an aliphatic unsaturated bond with a hydrosilane or organohydropolysiloxane having a Si-H bond in the presence of 11 catalyst,
13. A process for producing an alkane compound, characterized in that a compound having an aliphatic unsaturated bond is hydrogenated in the presence of 11 catalysts;
14 A method for producing an amine compound, wherein the amide compound is reduced with a silane or an organohydropolysiloxane having a Si—H bond in the presence of 11 catalysts;
15. An alcohol compound is produced by reducing an aldehyde compound, a ketone compound or an ester compound with a silane or an organohydropolysiloxane having a Si—H bond in the presence of 11 catalysts.

When the mononuclear ruthenium complex of the present invention is used as a catalyst and a hydrosilylation reaction between an aliphatic unsaturated group-containing compound and a Si—H group-containing silane or polysiloxane is carried out, the addition is performed at room temperature to 100 ° C. or less. The reaction becomes possible. Particularly, the addition reaction with industrially useful polysiloxane, trialkoxysilane and dialkoxysilane proceeds well. Furthermore, in the known literature, it is often shown that the reaction in which an unsaturated group-containing compound is generated by dehydrogenation silylation proceeds in preference to the addition reaction to the unsaturated group. When the catalyst of the invention is used, the addition reaction to the unsaturated group proceeds preferentially.
The hydrogenation reaction can be carried out under mild conditions at room temperature and 1 atm of hydrogen gas, and is also effective for the hydrogenation of multi-substituted alkenes, which was difficult with conventional methods. Further, the catalyst is resistant to temperature and pressure, and exhibits activity even under heating and pressurization conditions such as 80 ° C. or 10 atm.
In the reduction reaction of a carbonyl compound, the target reduction compound can be obtained by reacting an amide compound, an aldehyde compound, a ketone compound or an ester compound with a silane or polysiloxane having an Si—H group which is easy to handle. .

1 is a view showing a structure of a ruthenium complex A obtained in Example 1. FIG. 1 is a ¹ H-NMR spectrum diagram of a ruthenium complex A obtained in Example 1. FIG. 4 is a view showing a structure of a ruthenium complex B obtained in Example 2. FIG. 2 is a ¹ H-NMR spectrum diagram of a ruthenium complex B obtained in Example 2. FIG. 3 is a ¹ H-NMR spectrum diagram of a ruthenium complex C obtained in Example 3. FIG. 2 is a ¹ H-NMR spectrum diagram of a ruthenium complex D obtained in Example 4. FIG. 6 is a view showing a structure of a ruthenium complex E obtained in Example 5. FIG. ^{1 is} a ¹ H-NMR spectrum diagram of a ruthenium complex E obtained in Example 5. FIG. 6 is a view showing a structure of a ruthenium complex F obtained in Example 6. FIG. 2 is a ¹ H-NMR spectrum diagram of a ruthenium complex F obtained in Example 6. FIG.

Hereinafter, the present invention will be described in more detail.
The mononuclear ruthenium complex according to the present invention has two Ru—Si bonds as represented by the formula (1), and Ru contains two carbon atoms other than carbon monoxide (CO) and a thiourea ligand. It is a neutral or cationic divalent complex in which three or four electronic ligands L are coordinated.

In the formula (1), R ¹ to R ⁶ are each independently a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an organooxy group, a monoorganoamino group, a diorgano, which may be substituted with X. Represents an amino group, a monoorganophosphino group, a diorganophosphino group, a monoorganosilyl group, a diorganosilyl group, a triorganosilyl group, or an organothio group, or any one of R ¹ to R ³ and R ⁴ to R ⁶ X represents a halogen atom, an organooxy group, a monoorganoamino group, a diorganoamino group, or an organothio group.
The alkyl group may be linear, branched or cyclic, and the carbon number thereof is not particularly limited, but is preferably an alkyl having 1 to 30 carbons, more preferably 1 to 10 carbons. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosanyl group, etc. Linear or branched alkyl group; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, Such as cycloalkyl groups such as Kurononiru group.

The number of carbon atoms of the aryl group is not particularly limited, but is preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms. Specific examples thereof include phenyl, 1- Examples include naphthyl, 2-naphthyl, anthryl, phenanthryl, o-biphenylyl, m-biphenylyl, p-biphenylyl group and the like.
The number of carbon atoms of the aralkyl group is not particularly limited, but is preferably an aralkyl group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms. Specific examples thereof include benzyl and phenylethyl. , Phenylpropyl, naphthylmethyl, naphthylethyl, naphthylpropyl group and the like.

The organooxy group is not particularly limited, but RO (R is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms, or 7 to 30 carbon atoms. An alkoxy group, an aryloxy group, an aralkyloxy group, and the like represented by aralkyl group.
The alkoxy group is not particularly limited, but is preferably an alkoxy group having 1 to 30 carbon atoms, particularly 1 to 10 carbon atoms. Specific examples thereof include methoxy, ethoxy, n-propoxy, i-propoxy, c-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy group, etc. .
The aryloxy group is not particularly limited, but is preferably an aryloxy group having 6 to 30 carbon atoms, particularly 6 to 20 carbon atoms. Specific examples thereof include phenoxy, 1-naphthyloxy and 2-naphthyl. An oxy, anthryloxy, phenanthryloxy group, etc. are mentioned.
The aralkyloxy group is not particularly limited, but is preferably an aralkyloxy group having 7 to 30 carbon atoms, particularly 7 to 20 carbon atoms, and is preferably a benzyloxy group, phenylethyloxy, phenylpropyloxy, 1 or 2- Examples thereof include naphthylmethyloxy, 1 or 2-naphthylethyloxy, 1 or 2-naphthylpropyloxy group and the like.
Examples of the organothio group include groups in which the oxygen atom of the organooxy group is substituted with a sulfur atom.

The mono-organo groups include, but are not particularly limited, is preferably one represented by RNH ₂ (R represents the same meaning as above.) The preferred number of carbon atoms in R of the alkoxy, aryloxy, aralkyloxy Same as the group. Specific examples thereof include methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, s-butylamino, t-butylamino, n-pentylamino, n-hexylamino, n- Heptylamino, n-octylamino, n-nonylamino, n-decylamino, n-undecylamino, n-dodecylamino, n-tridecylamino, n-tetradecylamino, n-pentadecylamino, n-hexadecylamino A linear or branched monoalkylamino group such as n-heptadecylamino, n-octadecylamino, n-nonadecylamino, n-eicosanylamino group; cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclo Heptylamino, cyclooct Monocycloalkylamino groups such as ruamino and cyclononylamino groups; monoarylamino groups such as anilino, 1 or 2-naphthylamino groups; benzylamino, phenylethylamino, phenylpropylamino, 1 or 2-naphthylmethylamino groups, etc. And a monoaralkylamino group.

The diorganoamino group is not particularly limited, but is preferably represented by R ₂ NH (wherein R independently represents the same meaning as described above). , Aryloxy and aralkyloxy groups. Specific examples thereof include dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, diisobutylamino, di-s-butylamino, di-t-butylamino, di-n-pentyl. Amino, di-n-hexylamino, di-n-heptylamino, di-n-octylamino, di-n-nonylamino, di-n-decylamino, di-n-undecylamino, di-n-dodecylamino, Di-n-tridecylamino, di-n-tetradecylamino, di-n-pentadecylamino, di-n-hexadecylamino, di-n-heptadecylamino, di-n-octadecylamino, di-n -Nonadecylamino, di-n-eicosanylamino, N-ethylmethylamino, N-isopropylmethylamino, N-butylmethylamino Linear or branched dialkylamino groups such as di-groups; dicyclopropylamino, dicyclobutylamino, dicyclopentylamino, dicyclohexylamino, dicycloheptylamino, dicyclooctylamino, dicyclononylamino, cyclopentylcyclohexylamino groups, etc. A dicycloalkylamino group, an alkylarylamino group such as N-methylanilino, N-ethylanilino, Nn-propylanilino group; diphenylamino, 4,4'-bisnaphthylamino, N-phenyl-1 or 2- And diarylamino groups such as naphthylamino group; and diaralkylamino groups such as dibenzylamino, bis (phenylethyl) amino, bis (phenylpropyl) amino, and bis (1 or 2-naphthylmethyl) amino groups.

The monoorganophosphino group is not particularly limited, but is preferably RPH (where R represents the same meaning as described above), and the preferred carbon number in R is alkoxy, aryloxy, aralkyloxy. Same as the group. Specific examples thereof include methyl phosphino, ethyl phosphino, n-propyl phosphino, isopropyl phosphino, n-butyl phosphino, isobutyl phosphino, s-butyl phosphino, t-butyl phosphino, n-pentyl phosphino. Fino, n-hexylphosphino, n-heptylphosphino, n-octylphosphino, n-nonylphosphino, n-decylphosphino, n-undecylphosphino, n-dodecylphosphino, n-tridecylphosphino, n- Direct groups such as tetradecylphosphino, n-pentadecylphosphino, n-hexadecylphosphino, n-heptadecylphosphino, n-octadecylphosphino, n-nonadecylphosphino, n-eicosanylphosphino group, etc. Chain or branched monoalkylphosphino group; cyclopropylphosphine Monocycloalkyl phosphino groups such as ino, cyclobutyl phosphino, cyclopentyl phosphino, cyclohexyl phosphino, cycloheptyl phosphino, cyclooctyl phosphino, cyclononyl phosphino groups; phenyl phosphino, 1 or 2-naphthyl phosphino And monoarylphosphino groups such as fino groups; monoaralkylphosphino groups such as benzylphosphino groups and the like.

The diorganophosphino group is not particularly limited, but is preferably represented by R ₂ P (wherein R independently represents the same meaning as described above), and the preferred carbon number in R is the alkoxy group described above. , Aryloxy and aralkyloxy groups. Specific examples thereof include dimethylphosphino, diethylphosphino, di-n-propylphosphino, diisopropylphosphino, di-n-butylphosphino, diisobutylphosphino, di-s-butylphosphino, di-t- Butylphosphino, di-n-pentylphosphino, di-n-hexylphosphino, di-n-heptylphosphino, di-n-octylphosphino, di-n-nonylphosphino, di-n-decylphosphino, di- n-undecylphosphino, di-n-dodecylphosphino, di-n-tridecylphosphino, di-n-tetradecylphosphino, di-n-pentadecylphosphino, di-n-hexadecylphosphino Di-n-heptadecylphosphino, di-n-octadecylphosphino, di-n-nonadecylphosphino, di-n- Linear or branched dialkylphosphino group such as icosanylphosphino group; dicyclopropylphosphino, dicyclobutylphosphino, dicyclopentylphosphino, dicyclohexylphosphino, dicycloheptylphosphino, dicyclooctylphosphino A dicycloalkylphosphino group such as a dicyclononylphosphino group; an alkylarylphosphino group such as a cyclohexylphenylphosphino group; a diarylphosphino group such as a diphenylphosphino or bis (1 or 2-naphthyl) phosphino group; And diaralkylphosphino groups such as dibenzylphosphino, bis (phenylethyl) phosphino and bis (1 or 2-naphthylmethyl) phosphino groups.

Mono-organosilyl group, but are not particularly limited, but is preferably one represented by the RSiH ₂ (R has the same meaning as above.) The preferred number of carbon atoms in R of the alkoxy, aryloxy, aralkyloxy Same as the group. Specific examples thereof include methylsilyl, ethylsilyl, n-propylsilyl, isopropylsilyl, n-butylsilyl, isobutylsilyl, s-butylsilyl, t-butylsilyl, n-pentylsilyl, n-hexylsilyl, n-heptylsilyl, n- Octylsilyl, n-nonylsilyl, n-decylsilyl, n-undecylsilyl, n-dodecylsilyl, n-tridecylsilyl, n-tetradecylsilyl, n-pentadecylsilyl, n-hexadecylsilyl, n-heptadecyl Linear or branched monoalkylsilyl groups such as silyl, n-octadecylsilyl, n-nonadecylsilyl, n-eicosanylsilyl; cyclopropylsilyl, cyclobutylsilyl, cyclopentylsilyl, cyclohexylsilyl, cycloheptylsilyl, cyclooctyl Monocycloalkylsilyl groups such as rusilyl and cyclononylsilyl groups; monoarylsilyl groups such as phenylsilyl, 1 or 2-naphthylsilyl groups; benzylsilyl, phenylethylsilyl, phenylpropylsilyl, 1 or 2-naphthylmethylsilyl groups And monoaralkylsilyl groups such as

The diorgano silyl group is not particularly limited, is preferably one represented by R ₂ SiH (R independently of one another represent the same meaning as above.) The preferred number of carbon atoms in R of the alkoxy, The same as the aryloxy and aralkyloxy groups. Specific examples thereof include dimethylsilyl, diethylsilyl, di-n-propylsilyl, diisopropylsilyl, di-n-butylsilyl, diisobutylsilyl, di-s-butylsilyl, di-t-butylsilyl, di-n-pentylsilyl, Di-n-hexylsilyl, di-n-heptylsilyl, di-n-octylsilyl, di-n-nonylsilyl, di-n-decylsilyl, di-n-undecylsilyl, di-n-dodecylsilyl, di- n-tridecylsilyl, di-n-tetradecylsilyl, di-n-pentadecylsilyl, di-n-hexadecylsilyl, di-n-heptadecylsilyl, di-n-octadecylsilyl, di-n-nonadecylsilyl Di-n-eicosanylsilyl, ethylmethylsilyl, isopropylmethylsilyl, butylmethylsilyl groups, etc. Or a branched dialkylsilyl group; a dicycloalkylsilyl group such as dicyclopropylsilyl, dicyclobutylsilyl, dicyclopentylsilyl, dicyclohexylsilyl, dicycloheptylsilyl, dicyclooctylsilyl, dicyclononylsilyl, cyclopentylcyclohexylsilyl group, etc. Alkylalkylsilyl groups such as (methyl) phenylsilyl, (ethyl) phenylsilyl, (n-propyl) phenylsilyl groups; diphenylsilyl, bis (1 or 2-naphthyl) silyl, phenyl-1 or 2-naphthylsilyl groups And diarylsilyl groups such as dibenzylsilyl, bis (phenylethyl) silyl, bis (phenylpropyl) silyl, and bis (1 or 2-naphthylmethyl) silyl groups.

The triorganosilyl group, is not particularly limited, R ₃ Si (R represents. As defined above independently of each other) is preferably one represented by the preferable number of carbon atoms in R of the alkoxy, The same as the aryloxy and aralkyloxy groups. Specific examples thereof include trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl, triisobutylsilyl, tri-s-butylsilyl, tri-t-butylsilyl, tri-n-pentylsilyl. , Tri-n-hexylsilyl, tri-n-heptylsilyl, tri-n-octylsilyl, tri-n-nonylsilyl, tri-n-decylsilyl, tri-n-undecylsilyl, tri-n-dodecylsilyl, tri -N-tridecylsilyl, tri-n-tetradecylsilyl, tri-n-pentadecylsilyl, tri-n-hexadecylsilyl, di-n-heptadecylsilyl, di-n-octadecylsilyl, di-n- Nonadecylsilyl, tri-n-eicosanylsilyl, ethyldimethylsilyl, diisopropyl Linear or branched trialkylsilyl groups such as pyrmethylsilyl and dibutylmethylsilyl groups; tricyclopropylsilyl, tricyclobutylsilyl, tricyclopentylsilyl, tricyclohexylsilyl, tricycloheptylsilyl, tricyclooctylsilyl, tricyclo Tricycloalkylsilyl groups such as nonylsilyl groups; alkylarylsilyl groups such as (methyl) diphenylsilyl, (ethyl) diphenylsilyl, (n-propyl) diphenylsilyl groups; triphenylsilyl, tri (1 or 2-naphthyl) Triarylsilyl groups such as silyl, diphenyl-1 or 2-naphthylsilyl groups; tribenzylsilyl, tri (phenylethyl) silyl, tri (phenylpropyl) silyl, tri (1 or 2-naphthylmethyl) silyl groups, etc. And aralkyl silyl group.

Each of the above substituents may have at least one hydrogen atom on R substituted with a substituent X, where X is a halogen atom, an organooxy group, a monoorganoamino group, a diorganoamino group, or Examples include organothio groups, and examples of the organooxy group, monoorganoamino group, diorganoamino group, and organothio group include the same groups as described above.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms, but a fluorine atom is preferable, and examples of suitable fluorine-substituted alkyl groups include trifluoropropyl group, nonafluorohexyl group, heptadecylfluorodecyl group and the like. .

Among the above substituents, R ¹ to R ⁶ are each independently an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 7 to 7 carbon atoms that may be substituted with X. A 30 aralkyl group is preferable, and an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms are more preferable.

The crosslinking substituent in which at least one of R ¹ to R ³ and any one of R ⁴ to R ⁶ is bonded is not particularly limited as long as it is a substituent capable of crosslinking two Si atoms. For example, —O—, —S—, —NH—, —NR— (R is the same as above), —PR— (R is the same as above), —NH— (CH ₂ ) _k —NH -(K represents an integer of 1 to 10), -NR- (CH ₂ ) _k -NR- (k is the same as above, R is the same as above independently), -PH- (CH ₂ ) _K -PH- (k is the same as above), -PR- (CH ₂ ) _k -PR- (k is the same as above, R is independently the same as above), -C = C-, An alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 30 carbon atoms, an aralkylene group having 7 to 30 carbon atoms, — (CH ₂ O) _k — (k is the same as above). , — (CH ₂ ) _k —O— (CH ₂ ) _k — (k is the same as described above independently), —O— (CH ₂ ) _k —O— (R and k are the same as above) , —R′—O— (CH ₂ ) _k —O—R ′ — (R ′ is independently an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 30 carbon atoms, or 7 to 7 carbon atoms. 30 represents an aralkylene group, k is the same as described above.), — (CH ₂ S) _k — (k is the same as described above), — (CH ₂ ) _k —S— (CH ₂ ) _k — (k is Independently of each other as described above), —S— (CH ₂ ) _k —S— (k is as defined above), —R′—S— (CH ₂ ) _k —O—R ′ — (R ′ represents the same meaning as above independently of one another, k are as defined _{above), -. SiR 2 - (} R independently of one another represent the same meaning as _{above), -. (CH 2)} k -SiR 2 - (CH ₂₎ _k - R has the same meaning as above independently of each other, k is.) And the like represent the same meaning as above and the like independently of each other.

Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene and hexamethylene groups.
Examples of the arylene group having 6 to 30 carbon atoms include o-phenylene (1,2-phenylene), 1,2-naphthylene, 1,8-naphthylene and 2,3-naphthylene groups.
As the aralkylene group having 7 to 30 carbon atoms, — (CH ₂ ) _k —Ar— (Ar represents an arylene group having 6 to 20 carbon atoms, k represents the same meaning as described above), —Ar— ( CH ₂ ) _k — (Ar and k are as defined above), — (CH ₂ ) _k —Ar— (CH ₂ ) _k — (Ar is as defined above, and k is independently of each other. The same meaning as above).
In the alkylene, arylene, and aralkylene groups, at least one of those hydrogen atoms may be substituted with a substituent X (X is the same as above).

When the bridging substituent is represented as Z, the number of Z connecting two silicon atoms is 1 to 3, and a mononuclear ruthenium complex having such a bridging substituent Z is represented by the following formula.

(In the formula, R ¹ , R ² , R ⁵ , R ⁶ , L and m represent the same meaning as described above, and Z represents a bridging substituent.)

Specific examples of the disila metallacycle structure having a crosslinking substituent include those represented by the following formula, but are not limited thereto.

(In the formula, Me means a methyl group.)

In the formula, R ¹ , R ² , R ⁴ and R ⁵ represent the same meaning as described above, and R ¹⁷ to R ²⁰ (substituent Y) are each independently a hydrogen atom, a halogen atom, a carbon number of 1 to 10 represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and R ²⁵ to R ³⁰ each independently represent a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms. However, it is preferred that R ¹⁷ to R ²⁰ and R ²⁵ to R ³⁰ are hydrogen atoms.
Specific examples of the monovalent hydrocarbon group include an alkyl group, an aryl group, an aralkyl group, and the like, and specific examples thereof include those similar to the above.
Examples of the alkyl group, alkoxy group, and halogen atom are the same as those described above.

On the other hand, L is a two-electron ligand other than CO and a thiourea ligand in which two electrons contained in the ligand are coordinated to ruthenium.
The two-electron ligand is not particularly limited as long as it is other than CO and thiourea ligand, and any ligand conventionally used as the two-electron ligand of the metal complex may be used. Typically, amines, imines, nitrogen-containing heterocycles, phosphines, phosphites, arsines, alcohols, thiols, ethers, including unshared electron pairs (unpaired electrons) such as nitrogen, oxygen, sulfur, and phosphorus Compounds such as sulfides; Alkenes, alkynes containing π electrons; Compounds such as aldehydes, ketones, nitriles and isonitriles containing both unpaired and π electrons; Molecular hydrogen (H- Σ electrons contained in H bonds are coordinated), hydrosilane (σ electrons contained in Si—H bonds are coordinated), and the like.
In the present invention, the coordination number m of the two-electron ligand L is 3 or 4, but is preferably 4.

Examples of the amine include tertiary amines represented by R ₃ N (wherein R independently represents the same meaning as described above).
Examples of the imine include those represented by RC (= NR) R (wherein R independently represents the same meaning as described above).
Examples of the nitrogen-containing heterocycle include pyrrole, imidazole, pyridine, pyrimidine, oxazoline, isoxazoline and the like.
Examples of the phosphine include those represented by R ₃ P (R represents the same meaning as described above independently of each other).
Examples of the phosphite include those represented by (RO) ₃ P (R represents the same meaning as described above independently of each other).
Examples of the arsine include those represented by R ₃ As (wherein R independently represents the same meaning as described above).
As alcohol, what is shown by ROH (R represents the same meaning as the above.) Is mentioned, for example.
Examples of the thiol include those in which the oxygen atom of the alcohol is substituted with a sulfur atom.

Examples of the ether include those represented by ROR (wherein R independently represents the same meaning as described above).
Examples of the sulfide include those obtained by substituting the oxygen atom of the ether with a sulfur atom.
Examples of the ketone include those represented by RCOR (R represents the same meaning as described above independently of each other).
Examples of the isonitrile include those represented by RNC (R represents the same meaning as described above independently of each other).
Examples of the alkene include ethene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, cyclopentene, 1-hexene, cyclohexene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like. And alkenes having 2 to 30 carbon atoms.
Examples of the alkyne include, for example, ethyne, propyne, 1-butyne, 2-butyne, 1-pentyne, 2-pentyne, 1-hexyne, 1-heptin, 1-octyne, 1-nonine, 1-decyne, and the like. Up to 30 alkenes.
Examples of the hydrosilane include triorganohydrosilane, specifically, an organohydrosilane having 1 to 30 tricarbon atoms, and more specifically, R ¹ R ² R ³ SiH (where R ¹ to R ³ are the above-mentioned). It represents the same meaning as).

Among these, as the two-electron ligand L, molecular hydrogen, amine, imine, nitrogen-containing heterocycle, phosphine, phosphite, arsine, alcohol, thiol, ether, sulfide, nitrile, isonitrile, aldehyde, ketone, carbon Alkenes having 2 to 30 carbon atoms, alkynes having 2 to 30 carbon atoms, and triorganohydrosilane are preferable.

Note that two Ls may be bonded to each other to form a ligand containing two coordinating two-electron functional groups. Representative examples include, but are not limited to, ethylenediamine, ethylene glycol dimethyl ether, 1,3-butadiene, and those represented by the following formula.
However, in the mononuclear ruthenium complex of the present invention, when three or more L exist, a ligand containing three coordinating two-electron functional groups by bonding three of them, for example, η ⁶ − Does not have an arylene structure.

(In the formula, Me represents a methyl group and Ph represents a phenyl group. R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ and Z have the same meaning as described above.)

In the mononuclear ruthenium complex of the present invention, in view of catalytic activity, at least one of the two-electron ligand L is at least one selected from isonitrile, amine, imine, nitrogen-containing heterocycle, phosphine, phosphite and sulfide. It is preferable to be a seed, and when such a two-electron ligand is L ¹ , a mononuclear ruthenium complex represented by the formula (2) is preferable.

(R ¹ to R ⁶ represent the same meaning as described above.)

Here, as described above, L ¹ represents at least one dielectron ligand selected from isonitrile, amine, imine, nitrogen-containing heterocycle, phosphine, phosphite and sulfide, and among them, isonitrile, nitrogen-containing More preferably, it is at least one selected from a heterocycle, a phosphine, and a phosphite, even more preferably at least one selected from an isonitrile, a nitrogen-containing heterocycle, and a phosphite. Isonitriles with the same electronic configuration are optimal.
m ¹ represents an integer of 1 to 4, with 2 being preferred. When m ¹ is 2 to 4, two L ¹ may be bonded to each other.

Specific examples of isonitrile include those represented by RNC (wherein R represents the same meaning as described above) as described above. In particular, R is a substituted or unsubstituted carbon number. Preferred is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. A phenyl group having a substituent such as a group is even more preferable.
Usable isonitriles include methyl isocyanide, ethyl isocyanide, n-propyl isocyanide, cyclopropyl isocyanide, n-butyl isocyanide, isobutyl isocyanide, sec-butyl isocyanide, t-butyl isocyanide, n-pentyl isocyanide, isopentyl isocyanide, neo Alkyl isocyanides such as pentyl isocyanide, n-hexyl isocyanide, cyclohexyl isocyanide, cycloheptyl isocyanide, 1,1-dimethylhexyl isocyanide, 1-adamantyl isocyanide, 2-adamantyl isocyanide; phenyl isocyanide, 2-methylphenyl isocyanide, 4-methylphenyl Isocyanide, 2,4-dimethylphenyl isocyanide, 2,5-dimethylphenyl isocyanide 2,6-dimethylphenyl isocyanide, 2,4,6-trimethylphenyl isocyanide, 2,4,6-tri-t-butylphenyl isocyanide, 2,6-diisopropylphenyl isocyanide, 1-naphthyl isocyanide, 2-naphthyl isocyanide, Examples include aryl isocyanides such as 2-methyl-1-naphthyl isocyanide; aralkyl isocyanides such as benzyl isocyanide and phenylethyl isocyanide, but are not limited thereto.

Specific examples of the nitrogen-containing heterocycle are as described above, and among them, a pyridine ring is preferable.
Pyridine ring-containing compounds that can be used include pyridines such as pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-dimethylpyridine, 2,2'-bipyridine, 4,4'- Dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 4,4'-diethyl-2,2'-bipyridine, 4,4'-ditert-butyl-2,2 Examples include, but are not limited to, bipyridines such as' -bipyridine.

Examples of the phosphite include those represented by (RO) ₃ P (wherein R represents the same meaning as described above) as described above, and in particular, R is substituted or unsubstituted. An alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.
Usable phosphite compounds include trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, tris (2-ethylhexyl) phosphite, tri n-decyl phosphite, 4-methyl-2 , 6,7-trioxa-1-phosphabicyclo [2.2.2] octane (trimethylolethane cyclic phosphite), 4-ethyl-2,6,7-trioxa-1-phosphabicyclo [2. 2.2] trialkyl phosphites such as octane (trimethylolpropane phosphite), alkylaryl phosphites such as methyldiphenyl phosphite, and triaryl phosphites such as triphenyl phosphite. It is not limited to.

On the other hand, L ² represents a two-electron ligand other than CO, a thiourea ligand, and L ¹ , and specific examples thereof are the same as those described above for L. m ² represents an integer of 0 to 3, and 2 is preferable. Further, m ¹ + m ² satisfies 3 or 4 similarly to the above m, but is preferably 4. When m ² is 2 or 3, two L ² may be bonded to each other.

In the present invention, since the two-electron ligand L ² that binds to ruthenium relatively weakly is advantageous from the viewpoint of catalytic activity, among L exemplified above, thiol, sulfide, triorganohydrosilane are particularly preferred. In particular, SiHR ⁷ R ⁸ R ⁹ and SiHR ¹⁰ R ¹¹ R ¹² (R ⁷ to R ¹² independently of each other represent an alkyl group, an aryl group or an aralkyl group which may be substituted with X. X represents the same meaning as described above), SR ¹³ R ¹⁴ and SR ¹⁵ R ¹⁶ (R ¹³ to R ¹⁶ are each independently a hydrogen atom, X It represents an alkyl group, an aryl group or an aralkyl group which may be substituted, and X represents the same meaning as described above.
Here, specific examples of the alkyl group, the aryl group, and the aralkyl group include the same groups as those exemplified above, but each of the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 20 carbon atoms, Aralkyl groups having 7 to 20 carbon atoms are preferable, alkyl groups having 1 to 10 carbon atoms, and aryl groups having 6 to 20 carbon atoms are more preferable.

In the mononuclear ruthenium complex of the formula (2), for example, when L ¹ is 2 and L ² is 2 (they are distinguished as L ^2a and L ^2b ), the arrangement as shown by the following formula is used. Although there are coordinated structural isomers, the mononuclear ruthenium complex of the present invention includes all of these coordinated structural isomers.

(Wherein R ¹ to R ⁶ and L ¹ represent the same meaning as described above, and L ^2a and L ^2b represent the same meaning as L ² described above.)

When L ² is a triorganohydrosilane represented by SiHR ⁷ R ⁸ R ⁹ and SiHR ¹⁰ R ¹¹ R ¹² (R ⁷ to R ¹² have the same meaning as above), a mononuclear ruthenium complex is formed. Two or more of the four silicon atoms may be connected by the above-described bridging substituent Z. The combination of silicon atoms is silicon atoms having silicon-ruthenium covalent bonds, silicon atoms coordinated by Si—H, silicon-ruthenium covalent bonds, and silicon atoms coordinated by Si—H. Either of these may be used. In this case, the number of Z connecting two silicon atoms is 1 to 3, while the total number of Z contained in the whole complex is 1 to 12.
When the mononuclear ruthenium complex having such a bridging substituent Z is expressed using one coordination structure, the structure shown by the following formula is exemplified, but is not limited thereto, As described above, there are other coordination structural isomers, and there are also structures having the same bridging substituent Z.

(In the formula, R ¹ to R ¹² , L ¹ and Z have the same meaning as described above.)

Specific examples of the structure of the mononuclear ruthenium complex having a disila metallacycle structure include those represented by the following formula (expressed excluding L ¹ ), but are not limited thereto.

(In the formula, Me means a methyl group.)

In particular, in the present invention, a mononuclear ruthenium complex in which two L ¹ are coordinated and Si—H of a triorganohydrosilane which is a two-electron ligand is agogotically coordinated is preferable. When such a ruthenium complex is expressed conveniently using one coordination structure, a structure represented by the formula (3) can be given. As described above, in the present invention, other coordination structure isomerism is used. It may be a body.

(In the formula, L ¹ represents the same meaning as described above.)

In formula (3), R ¹ to R ¹² represent the same meaning as described above, but R ¹ to R ⁶ may be independently substituted with X (X represents the same meaning as described above). Preferred are an alkyl group, an aryl group or an aralkyl group.
Here, specific examples of the alkyl group, the aryl group, and the aralkyl group include the same groups as those exemplified above, but each of the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 20 carbon atoms, Aralkyl groups having 7 to 20 carbon atoms are preferable, alkyl groups having 1 to 10 carbon atoms, and aryl groups having 6 to 20 carbon atoms are more preferable.
Also in the above formula (3), two or more of the four silicon atoms constituting the mononuclear ruthenium complex may be connected by a bridging substituent, specifically, any one of R ¹ to R ³ and R ^At least one of any of ⁴ to R ⁶ or at least one of any of R ⁷ to R ⁹ together, or any of R ¹⁰ to R ¹² and at least any of R ⁴ to R ⁶ One set or at least one of R ⁷ to R ⁹ may be combined together to form a bridging substituent such as an alkylene group, an arylene group or an aralkylene group, or any one of R ¹ to R ³ ; At least one group of any of R ⁴ to R ⁶ or at least one group of any of R ⁷ to R ⁹ together forms a bridging substituent such as an alkylene group, an arylene group or an aralkylene group, and R ¹⁰ one of the ~ R ¹² When, also form one of the at least one pair and R ⁷ ~ either at least one set alkylene group together, bridging substituent such as an arylene group or an aralkylene group R ⁹ in R ⁴ ~ R ⁶ Good.
Here, specific examples of the alkylene group, the arylene group, and the aralkylene group include the same groups as those exemplified above. However, the alkylene group having 1 to 10 carbon atoms, the arylene group having 7 to 20 carbon atoms, Aralkylene groups having 7 to 20 carbon atoms are preferable, alkylene groups having 1 to 6 carbon atoms, and arylene groups having 7 to 20 carbon atoms are more preferable.

When a mononuclear ruthenium complex that can be suitably used in the present invention is represented by using a typical coordination structure, one represented by the formula (4) or (5) can be mentioned, specifically, the formula (6) To those represented by (11), more specifically those represented by A to F, but are not limited thereto, and as described above, these coordination structure isomers. Can also be suitably used.

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ , R ¹⁷ to R ²⁰ and L ¹ represent the same meaning as described above.)

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ and R ¹⁷ to R ²⁰ have the same meaning as described above, and Me represents a methyl group.)

(In the formula, Me means a methyl group.)

The mononuclear ruthenium complex of the present invention can be produced by combining known organic synthesis reactions.
For example, the ruthenium complexes A to F are ruthenium-olefin complexes having a cycloalkadienyl group such as a cyclohexadienyl group or a cyclooctadienyl group and an alkenyl group such as an allyl group or a 2-methylallyl group as a ligand. Reaction of bissilyl compounds such as 1,2-bis (dimethylsilyl) benzene and isonitrile compounds such as t-butylisocyanide, phosphite compounds, or bipyridine compounds in an organic solvent under an inert gas atmosphere such as argon gas Can be obtained.
In this case, the amount of the bissilyl compound to be used can be about 1 to 10 mol times, preferably 2 to 5 mol times based on the ruthenium-olefin complex.
The amount of the isonitrile compound, phosphite compound, and bipyridine compound used can be about 1 to 10 moles, preferably 2 to 5 moles, relative to the ruthenium-olefin complex.
As the organic solvent, various solvents can be used as long as they do not affect the reaction. For example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane; diethyl ether, diisopropyl ether, dibutyl ether , Ethers such as cyclopentyl methyl ether, tetrahydrofuran and 1,4-dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene can be used.
The reaction temperature may be appropriately set within the range from the melting point to the boiling point of the organic solvent, but is preferably 10 to 100 ° C, more preferably 30 to 80 ° C.
The reaction time is usually about 1 to 48 hours.
After completion of the reaction, the solvent can be distilled off, and then the desired product can be obtained by a known purification method such as recrystallization, but the prepared ruthenium complex can be used as a catalyst for the desired reaction without isolation. Also good.

As described above, the mononuclear ruthenium complex of the present invention exhibits catalytic activity in any one or more of hydrosilylation reaction, hydrogenation reaction, and reduction reaction of carbonyl compound, but has catalytic activity in two reactions. Some of them exhibit catalytic activity in all three reactions.
Using the mononuclear ruthenium complex of the present invention as a catalyst and having an aliphatic unsaturated bond, such as an olefin compound, a silane compound or an organopolysiloxane compound, and a compound having an aliphatic unsaturated bond, and an Si—H bond In the hydrosilylation reaction with a silane compound or an organopolysiloxane compound, the amount of the catalyst used is not particularly limited, but the reaction is allowed to proceed under mild conditions of room temperature to about 100 ° C. with good yield. In consideration of obtaining the desired product, the amount of the catalyst used is preferably 0.005 mol% or more.
Even when the mononuclear ruthenium complex of the present invention is used as a catalyst and an olefinic compound containing an aliphatic unsaturated bond is reduced with hydrogen gas to obtain a saturated compound, the amount of the catalyst used is particularly limited. However, considering that the desired product is obtained in good yield by proceeding the reaction at room temperature and under a mild condition where the hydrogen pressure is about 1 atm, the amount of the catalyst used is 0.05 mol% or more. It is preferable to do.

Even when the mononuclear ruthenium complex of the present invention is used as a catalyst and the carbonyl compound is reduced with a silane or siloxane containing a Si—H group, the amount of the catalyst used is not particularly limited. In consideration of obtaining the desired product in good yield by advancing the reaction, the amount of the catalyst used is preferably 0.1 mol% or more.
Examples of the carbonyl compound that can be subjected to the reduction reaction include compounds having an amide, aldehyde, ketone, ester, carboxylic acid, carboxylate (for example, sodium salt, potassium salt, etc.) group, etc., and these are the ruthenium complex of the present invention. By reacting with a silane or siloxane containing a Si—H group in the presence of a catalyst, it can be led to the corresponding amine or alcohol compound, respectively.
In any reaction, the upper limit of the amount of catalyst used is not particularly limited, but is about 5 mol% from an economical viewpoint.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example.
The synthesis of the ruthenium complex was carried out using an Schlenk technique or a glove box in an argon atmosphere, and all the solvents used for the preparation of the transition metal compounds were used after deoxygenation and dehydration by known methods. .
Alkyne hydrosilylation reaction, hydrogenation reaction, amide reduction reaction and solvent purification are all carried out in an inert gas atmosphere. What was performed was used.
Measurement of ¹ H, ¹³ C, ²⁹ Si-NMR was performed using JNM-ECA600 and JNM-LA400 manufactured by JEOL Ltd., IR measurement was performed using FT / IR-550 manufactured by JASCO Corporation, and elemental analysis was manufactured by Perkin Elmer. X-ray crystal structure analysis of 2400II / CHN was performed using Rigaku Co., Ltd. VariMax and MoKα radiation 0.71069 angstroms, respectively.
In the chemical structural formulas shown below, hydrogen atoms are omitted according to a conventional expression. Me represents a methyl group.

(1) Synthesis of ruthenium complex [Example 1] Synthesis of ruthenium complex A

(Η ⁴ -1,5-cyclooctadiene) ruthenium (II) bis (η ³ -2-methylallyl) complex (200 mg, 0.63 mmol), 1,2-bis (dimethyl) was added to a 100 mL Schlenk tube under an argon atmosphere. Cyril) benzene (243 mg, 1.26 mmol) and t-butylisocyanide (104 mg, 1.26 mmol) were charged, and degassed / dehydrated hexane (30 mL) was added thereto, followed by stirring at 55 ° C. for 18 hours. After completion of the reaction, the reaction mixture was dried under reduced pressure, and the resulting dried product was dissolved in hexane (40 mL), and a small amount of brown insoluble matter by-produced by centrifugation was removed. Thereafter, the hexane solution is dried under reduced pressure, washed with hexamethyldisiloxane (10 mL), the remaining white powder is dissolved in 10 mL of hexane, and recrystallized at −35 ° C. to be representative of the ruthenium complex represented by the above formula. A (49 mg / 0.08 mmol / 12%) was obtained. The structure of the resulting ruthenium complex A is shown in FIG. 1, and the measurement result of ¹ H-NMR is shown in FIG.

¹ H NMR (C ₆ D ₆ , 600 MHz) δ = −7.64 (br s, 2H, Si—H), 0.59 (s, 18H, CMe ₃ ), 0.94 (s, 24H, SiMe ₂ ), 7.33-7.38 (m, 4H, C ₆ H ₄ ), 7.81-7.86 (m, 4H, C ₆ H ₄ ).
¹³ Si NMR (C ₆ D ₆ , 119 MHz) δ = 27.2.
IR (KBr pellet): ν = 1930 (ν _Si-H ), 2116 (ν _Ru-CN ) cm ⁻¹
Anal. Calcd. _{_{_{for C 30 H 52 N 2 RuSi}}} 4: C, 55.08; H, 8.01; N, 4.28 Found: C, 55.21; H, 7.89; N, 4.01

[Example 2] Synthesis of ruthenium complex B

(Η ⁴ -1,5-cyclooctadiene) ruthenium (II) bis (η ³ -2-methylallyl) complex (200 mg, 0.63 mmol), 1,2-bis (dimethyl) was added to a 100 mL Schlenk tube under an argon atmosphere. Silyl) benzene (243 mg, 1.26 mmol) and 1-isocyanoadamantane (203 mg, 1.26 mmol) were charged, and degassed / dehydrated hexane (30 mL) was added thereto, followed by stirring at 55 ° C. for 18 hours. After completion of the reaction, the reaction mixture was dried under reduced pressure, and the resulting dried product was dissolved in hexane (40 mL), and a small amount of brown insoluble matter by-produced by centrifugation was removed. Thereafter, the hexane solution is dried under reduced pressure, washed with hexamethyldisiloxane (10 mL), the remaining white powder is dissolved in 10 mL of hexane, and recrystallized at −35 ° C. to be representative of the ruthenium complex represented by the above formula. B (51 mg / 0.06 mmol / 10%) was obtained. The structure of the obtained ruthenium complex B is shown in FIG. 3, and the measurement result of ¹ H-NMR is shown in FIG.

¹ H NMR (C ₆ D ₆ , 600 MHz) δ = −7.62 (br s, 2H, Si—H), 0.93-1.09 (m, 12H, CH ₂ ), 1.04 (s, 24H, SiMe ₂ ), 1.38-1.44 (brs, 18H, CH ₂ and CH of adamantyl) 7.34-7.41 (m, 4H, C ₆ H ₄ ), 7.87-7. 92 (m, 4H, C ₆ H ₄ ).
¹³ Si NMR (C ₆ D ₆ , 119 MHz) δ = 21.1.
IR (KBr pellet): ν = 1927 (ν _Si-H ), 2118 (ν _Ru-CN ) cm ⁻¹
Anal. Calcd. _{_{_{for C 42 H 64 N 2 RuSi}}} 4: C, 62.25; H, 7.96; N, 3.46 Found: C, 62.53; H, 8.24; N, 3.22

[Example 3] Synthesis of ruthenium complex C

(Η ⁴ -1,5-cyclooctadiene) ruthenium (II) bis (η ³ -2-methylallyl) complex (200 mg, 0.63 mmol), 1,2-bis (dimethyl) was added to a 100 mL Schlenk tube under an argon atmosphere. Silyl) benzene (243 mg, 1.26 mmol) and 2,4,6-trimethylphenyl isocyanide (183 mg, 1.26 mmol) were charged, and degassed / dehydrated hexane (30 mL) was added thereto. Stir for hours. After completion of the reaction, the reaction mixture was dried under reduced pressure, and the resulting dried product was dissolved in toluene (40 mL), and a small amount of brown insoluble material by-produced by centrifugation was removed. Thereafter, the toluene solution was dried under reduced pressure, washed with hexane (10 mL), the remaining white powder was dissolved in 5 mL of toluene, recrystallized at -35 ° C., and ruthenium complex C represented by the above formula (74 mg). /0.09 mmol / 10%). FIG. 5 shows the measurement results of ¹ H-NMR of the obtained ruthenium complex C.

¹ H NMR (C ₆ D ₆ , 600 MHz) δ = −7.05 (br s, 2H, Si—H), 1.02 (s, 24H, SiMe ₂ ), 1.75 (s, 6H, para- Me of C ₆ H ₂ Me ₃ ), 1.76 (s, 12H, ortho-Me of C ₆ H ₂ Me ₃ ), 6.20 (s, 4H, C ₆ H ₂ Me ₃ ), 7.36- 7.39 (m, 4H, C ₆ H ₄ ), 7.81-7.85 (m, 4H, C ₆ H ₄ ).
IR (KBr pellet): ν = 1919 (ν _Si-H ), 2082 (ν _Ru-CN ) cm ⁻¹
Anal. Calcd. for C ₄₀ H ₅₆ N ₂ RuSi ₄ : C, 61.73; H, 7.25; N, 3.60 Found: C, 61.86; H, 7.02; N, 3.82

[Example 4] Synthesis of ruthenium complex D

(Η ⁴ -1,5-cyclooctadiene) ruthenium (II) bis (η ³ -2-methylallyl) complex (200 mg, 0.63 mmol), 1,2-bis (dimethyl) was added to a 100 mL Schlenk tube under an argon atmosphere. Cyril) benzene (243 mg, 1.26 mmol) and 2,6-diisopropylphenyl isocyanide (236 mg, 1.26 mmol) are charged, and degassed / dehydrated hexane (30 mL) is added thereto, followed by stirring at 55 ° C. for 18 hours. did. After completion of the reaction, the reaction mixture was dried under reduced pressure, and the resulting dried product was dissolved in tetrahydrofuran (40 mL, hereinafter, THF) to remove a small amount of brown insoluble material by-produced by centrifugation. Thereafter, the toluene solution was dried under reduced pressure, washed with hexane (10 mL), the remaining white powder was dissolved in 5 mL of THF, recrystallized at -35 ° C., and ruthenium complex D (60 mg / kg) represented by the above formula. 0.07 mmol / 11%). The measurement result of ¹ H-NMR of the obtained ruthenium complex D is shown in FIG.

¹ H NMR (C ₆ D ₆ , 600 MHz) δ = −7.09 (br s, 2H, Si—H), 0.78 (d, J _HH = 6.9 Hz, 24H, CH Me ₂ ), 0. 99 (s, 24H, SiMe ₂ ), 2.92 (sept, J _HH = 6.9 Hz, 4H, C H Me ₂ ), 6.70 (d, J _HH = 6.9 Hz, 4H, meta-C ₆ H ₃ ), 6.82 (t, J _HH = 6.9 Hz, 2H, para-C ₆ H ₃ ), 7.32-7.36 (m, 4H, C ₆ H ₄ ), 7.78-7 .83 (m, 4H, C ₆ H ₄ ).
IR (KBr pellet): ν = 1927 (ν _Si-H ), 2081 (ν _Ru-CN ) cm ⁻¹
Anal. Calcd. for C ₄₆ H ₆₈ N ₂ RuSi ₄ : C, 64.06; H, 7.95; N, 3.25 Found: C, 63.87; H, 8.34; N, 3.62

[Example 5] Synthesis of ruthenium complex E

(Η ⁴ -1,5-cyclooctadiene) ruthenium (II) bis (η ³ -2-methylallyl) complex (200 mg, 0.63 mmol), 1,2-bis (dimethyl) was added to a 100 mL Schlenk tube under an argon atmosphere. Cyril) benzene (243 mg, 1.26 mmol) and trimethylolpropane phosphite (204 mg, 1.26 mmol) were charged, and degassed / dehydrated hexane (30 mL) was added thereto, followed by stirring at 55 ° C. for 18 hours. After completion of the reaction, the reaction mixture was dried under reduced pressure, and the resulting dried product was dissolved in toluene (40 mL), and a small amount of brown insoluble material by-produced by centrifugation was removed. Thereafter, the toluene solution was dried under reduced pressure, washed with hexane (10 mL), the remaining white powder was dissolved in 10 mL of toluene, recrystallized at -35 ° C., and ruthenium complex E (61 mg represented by the above formula). /0.08 mmol / 12%). FIG. 7 shows the structure of the obtained ruthenium complex E, and FIG. 8 shows the measurement result of ¹ H-NMR.

¹ H NMR (C ₆ D ₆ , 600 MHz) δ = −8.52 (t, J _HP = 12.6 Hz, 2H, Si—H), −0.16 (t, J _HH = 6.9 Hz, 6H, _{_{CH 2 C H 3), 0.06}} (q, J HH = 6.9Hz, 4H, C H 2 CH 3), 1.13 (s, 24H, SiMe 2), 3.03 (s, 12H, OCH ₂ ), 7.28-7.34 (m, 4H, C ₆ H ₄ ), 7.81-7.86 (m, 4H, C ₆ H ₄ ).
¹³ Si NMR (C ₆ D ₆ , 119 MHz) δ = 27.7

[Example 6] Synthesis of ruthenium complex F

(Η ⁴ -1,5-cyclooctadiene) ruthenium (II) bis (η ³ -2-methylallyl) complex (200 mg, 0.63 mmol), 1,2-bis (dimethyl) was added to a 100 mL Schlenk tube under an argon atmosphere. Silyl) benzene (243 mg, 1.26 mmol) and 4,4′-di-t-butyl-2,2′-bipyridine (169 mg, 0.63 mmol) were charged, and degassed and dehydrated hexane (30 mL) And stirred at 55 ° C. for 18 hours. After completion of the reaction, the reaction mixture was dried under reduced pressure, and the resulting dried product was dissolved in toluene (50 mL), and a small amount of brown insoluble material by-produced by centrifugation was removed. Thereafter, the toluene solution was dried under reduced pressure, washed with hexane (10 mL), the remaining red powder was dissolved in 30 mL of toluene, recrystallized at −35 ° C., and ruthenium complex F represented by the above formula (67 mg). /0.09 mmol / 14%). The structure of the obtained ruthenium complex F is shown in FIG. 9, and the measurement result of ¹ H-NMR is shown in FIG.

¹ H NMR (C ₆ D ₆ , 600 MHz) δ = −11.2 (t, J _H-Si = 12.4 Hz, 2H, Si—H), −0.07 to 1.05 (br s, 24H, SiMe ₂ ), 0.87 (s, 18H, C (CH ₃ ) ₃ ), 6.45 (d, J _HH = 6.9 Hz, 2H, C ₅ H ₃ N), 7.21-7.27 ( m, 4H, C ₆ H ₄ ), 7.58-7.70 (br s, 4H, C ₆ H ₄ ), 8.00 (s, 2H, C ₅ H ₃ N), 8.53 (d, J _HH = 6.9 Hz, 2 H, C ₅ H ₃ N).
¹³ Si NMR (C ₆ D ₆ , 119 MHz) δ = 13.2.
IR (KBr pellet): ν = 2028 (ν _Si-H ) cm ^-1
Anal. Calcd. for C ₃₈ H ₅₈ N ₂ RuSi ₄ : C, 60.35; H, 7.73; N, 3.70 Found: C, 60.03; H, 7.56; N, 3.46

(2) Hydrosilylation of styrene with 1,1,1,3,3-pentamethyldisiloxane using ruthenium complex

[Example 7] Hydrosilylation reaction using ruthenium complex A A magnetic stirrer was added to a 20 mL Schlenk tube, and the mixture was heated and dried while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex A (6.5 mg, 0.01 mmol) was added to the Schlenk tube as a catalyst. Styrene (104 mg, 1.0 mmol) was added thereto, and 1,1,1,3,3-pentamethyldisiloxane (163 mg.1.1 mmol) was further added, and the solution was stirred at 25 ° C. for 23 hours. After cooling, anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 1 as entry 1.

1,1,1,3,3-pentamethyl-3- (2-phenylethyl) -disiloxane (the above compound (I))
¹ H NMR (400 MHz, CDCl ₃ ) δ = −0.03 (s, 6H, Si (C H ₃ ) ₂ ), −0.02 (s, 9H, Si (C H ₃ ) ₃ ), 0.775 −0.81 (m, 2H, SiC H ₂ ), 2.52 to 2.57 (m, 2H, C H ₂ C ₆ H ₅ ), 7.09-7.13 (m, 2H, C ₆ H _{5), 7.17-7.22 (m, 3H} , C 6 H 5).
1,1,1,3,3-pentamethyl-3-[(1E) -2-phenylethylene] -disiloxane (compound (II) above)
¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.11 (s, 6H, Si (CH ₃ ) ₂ ), 0.22 (s, 9H, Si (CH ₃ ) ₃ ), 6.42 (d, J _HH = 19.3 Hz, 1H, -CH = CH-), 6.93 (d, J _HH = 19.3 Hz, 1H, -CH = CH-), 7.24-7.29 (m, 1H, C _{_{6 H 5), 7.31-7.39 (m}} , 2H, C 6 H 5), 7.43-7.47 (m, 2H, C 6 H 5).
Ethylbenzene (the above compound (III))
¹ H NMR (400 MHz, CDCl ₃ ) δ = 1.26 (t, 2H, J _HH = 7.7 Hz, CH ₃ ), 2.67 (q, 2H, J _HH = 7.7 Hz, CH ₂ ), 7 .16-7.24 (m, 3H, C ₆ H ₅ ), 7.27-7.33 (m, 2H, C ₆ H ₅ ).

[Example 8] Hydrosilylation reaction using ruthenium complex B A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex B (2.4 mg, 0.003 mmol) was added to the Schlenk tube as a catalyst. Styrene (104 mg, 1.0 mmol) was added thereto, and 1,1,1,3,3-pentamethyldisiloxane (163 mg.1.1 mmol) was further added, and the solution was stirred at 25 ° C. for 23 hours. After cooling, anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 1 as entry 2.

[Example 9] Hydrosilylation reaction using ruthenium complex C A magnetic stirrer was added to a 20 mL Schlenk tube, dried by heating while reducing the pressure to 5 Pa, and the inside of the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (2.3 mg, 0.003 mmol) was added to the Schlenk tube as a catalyst. Styrene (104 mg, 1.0 mmol) was added thereto, and 1,1,1,3,3-pentamethyldisiloxane (163 mg.1.1 mmol) was further added, and the solution was stirred at 25 ° C. for 23 hours. After cooling, anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 1 as entry 3.

[Example 10] Hydrosilylation reaction using ruthenium complex D A magnetic stirrer was added to a 20 mL Schlenk tube, dried by heating while reducing the pressure to 5 Pa, and the inside of the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex D (0.9 mg, 0.001 mmol) was added to the Schlenk tube as a catalyst. Styrene (1040 mg, 10 mmol) was added thereto, and 1,1,1,3,3-pentamethyldisiloxane (1630 mg, 11 mmol) was further added thereto, and then the solution was stirred at 25 ° C. for 23 hours. After cooling, anisole (1080 mg, 10 mmol) was added as an internal standard, and a ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 1 as entry 4.

[Example 11] Hydrosilylation reaction using ruthenium complex F A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex F (2.3 mg, 0.003 mmol) was added to the Schlenk tube as a catalyst. Styrene (104 mg, 1.0 mmol) was added thereto, and 1,1,1,3,3-pentamethyldisiloxane (163 mg.1.1 mmol) was further added, and the solution was stirred at 25 ° C. for 23 hours. After cooling, anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 1 as entry 5.

(3) Hydrosilylation of styrene with dimethylphenylsilane using ruthenium complex

[Example 12] Hydrosilylation reaction using ruthenium complex A A magnetic stirrer was added to a 20 mL Schlenk tube, dried by heating while reducing the pressure to 5 Pa, and the inside of the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex A (3.2 mg, 0.005 mmol) was added to the Schlenk tube as a catalyst. Styrene (1040 mg, 10 mmol) was added thereto, dimethylphenylsilane (1500 mg, 11 mmol) was further added, and the solution was stirred at 25 ° C. for 23 hours. After cooling, anisole (1080 mg, 10 mmol) was added as an internal standard, and a ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 2 as entry 1.

[Dimethyl (2-phenylethyl) silyl] -benzene (the above compound (I))
¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.19 (s, 6H, Si (C H ₃ ) ₂ ), 0.98-1.07 (m, 2H, SiCH ₂ ), 2.49-2. 59 (m, 2H, C H ₂ C ₆ H ₅ ), 7.02-7.11 (m, 3H, C ₆ H ₅ ), 7.12-7.16 (m, 2H, C ₆ H ₅ ) 7.24-7.31 (m, 3H, C ₆ H ₅ ), 7.39-7.47 (m, 2H, C ₆ H ₅ ).
[Dimethyl [(1E) -2-phenylethylene] silyl] -benzene (the above compound (II))
¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.17 (s, 6H, Si (C H ₃ ) ₂ ), 6.49 (d, J _HH = 19.3 Hz, 1 H, SiC H ═CH—), 7.01-7.09 (m, 3H, C ₆ H ₅ ), 7.12-7.15 (m, 3H, C ₆ H ₅ and SiCH = C H- ), 7.25-7.32 ( _{_{m, 3H, C 6 H 5}} ), 7.37-7.46 (m, 2H, C 6 H 5).

[Example 13] Hydrosilylation reaction using ruthenium complex C A magnetic stirrer was added to a 20 mL Schlenk tube, dried by heating while reducing the pressure to 5 Pa, and the inside of the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (3.9 mg, 0.005 mmol) was added to the Schlenk tube as a catalyst. Styrene (1040 mg, 10 mmol) was added thereto, dimethylphenylsilane (1500 mg, 11 mmol) was further added, and the solution was stirred at 25 ° C. for 23 hours. After cooling, anisole (1080 mg, 10 mmol) was added as an internal standard, and a ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 2 as entry 2.

[Example 14] Hydrosilylation reaction using ruthenium complex D A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex D (0.9 mg, 0.001 mmol) was added to the Schlenk tube as a catalyst. Styrene (1040 mg, 10 mmol) was added thereto, dimethylphenylsilane (1500 mg, 11 mmol) was further added, and the solution was stirred at 25 ° C. for 23 hours. After cooling, anisole (1080 mg, 10 mmol) was added as an internal standard, and a ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 2 as entry 3.

[Example 15] Hydrosilylation reaction using ruthenium complex E A magnetic stirrer was added to a 20 mL Schlenk tube and heated and dried while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex E (8.1 mg, 0.01 mmol) was added to the Schlenk tube as a catalyst. Styrene (104 mg, 1.0 mmol) was added thereto, dimethylphenylsilane (150 mg, 1.1 mmol) was further added, and the solution was stirred at 25 ° C. for 23 hours. After cooling, anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 2 as entry 4.

(4) Hydrosilylation of 1-octene with 1,1,1,3,3-pentamethyldisiloxane using ruthenium complex

[Example 16] Hydrosilylation of 1-octene with 1,1,1,3,3-pentamethyldisiloxane A magnetic stirrer was added to a 20 mL Schlenk tube, and the mixture was heated and dried while reducing the pressure to 5 Pa. Was replaced with an argon atmosphere. Ruthenium complex A (2.0 mg, 0.003 mmol) was added to the Schlenk tube as a catalyst. 1-octene (112 mg, 1.0 mmol) was added thereto, and 1,1,1,3,3-pentamethyldisiloxane (163 mg, 1.1 mmol) was further added thereto, and then the solution was stirred at 80 ° C. for 23 hours. did. After cooling, anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 3 as entry 1.

[Example 17] Hydrosilylation reaction using ruthenium complex B A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex B (2.4 mg, 0.003 mmol) was added to the Schlenk tube as a catalyst. 1-octene (112 mg, 1.0 mmol) was added thereto, and 1,1,1,3,3-pentamethyldisiloxane (163 mg, 1.1 mmol) was further added thereto, and then the solution was stirred at 25 ° C. for 23 hours. did. After cooling, anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 3 as entry 2.

[Example 18] Hydrosilylation reaction using ruthenium complex C A magnetic stirrer was added to a 20 mL Schlenk tube, dried by heating while reducing the pressure to 5 Pa, and the inside of the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (2.3 mg, 0.003 mmol) was added to the Schlenk tube as a catalyst. 1-octene (112 mg, 1.0 mmol) was added thereto, and 1,1,1,3,3-pentamethyldisiloxane (163 mg, 1.1 mmol) was further added thereto, and then the solution was stirred at 25 ° C. for 23 hours. did. After cooling, anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 3 as entry 3.

[Example 19] Hydrosilylation reaction using ruthenium complex D A magnetic stirrer was added to a 20 mL Schlenk tube, dried by heating while reducing the pressure to 5 Pa, and the inside of the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex D (4.3 mg, 0.005 mmol) was added to the Schlenk tube as a catalyst. 1-octene (112 mg, 1.0 mmol) was added thereto, and 1,1,1,3,3-pentamethyldisiloxane (163 mg, 1.1 mmol) was further added thereto, and then the solution was stirred at 80 ° C. for 23 hours. did. After cooling, anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 3 as entry 4.

1,1,1,3,3-pentamethyl-3-octyl-disiloxane (Compound (I) above)
¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.03 (s, 6H, Si (C H ₃ ) ₂ ), 0.06 (s, 9H, Si (C H ₃ ) ₃ ), 0.45-0 .55 (m, 2H, SiC H 2), 0.88 (t, J HH = 7.2Hz, 3H, CH 2 C H 3), 1.20-1.34 (m, 12H, (C H 2 ₆ ).
1,1,1,3,3-pentamethyl-3- (1E) -1-octen-1-yl-disiloxane (compound (II) above)
¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.09 (s, 9H, Si (C H ₃ ) ₃ ), 0.12 (s, 6H, Si (C H ₃ ) ₂ ), 0.90 (t , 3H, J _HH = 7.6 Hz), 1.30-1.41 (m, 8H, C H ₂ ), 2.11 (q, 2H, J _HH = 7.6 Hz, C H ₂ -CH = CH ), 5.6 (d, 1H, J _HH = 18.2 Hz, Si—C H = CH), 6.11 (dt, 1 H, J _HH = 18.2 Hz, Si—CH = C H )
1,1,1,3,3-pentamethyl- (2E) -2-octen-1-yl-disiloxane (compound (III) above)
¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.08 (s, 9H, Si (C H ₃ ) ₃ ), 0.14 (s, 6H, Si (C H ₃ ) ₂ ), 0.88 (t , 3H, J _HH = 7.6 Hz), 1.28-1.42 (m, 8H, CH ₂ ), 2.12 (q, 2H, J _HH = 7.6 Hz, C H ₂ -CH = CH) , 5.15-5.46 (m, 2H, Si -CH 2 -C H = CH).
2-octene (compound (IV) above)
¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.90 (t, J _HH = 7.2 Hz, 3H, CH ₃ ), 1.11-1.51 (m, 4H, — (CH ₂ ) ₆ —) , 1.54-1.62 (m, 5H, — (CH ₂ ) ₆ -and C H ₃ —CH═CH), 2.03 (m, 2H, —C H ₂ —CH═CH), 5. 19-5.66 (m, 2H, CH ₃ -C H = CH),
n-octane (compound (V) above)
¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.88 (t, J _HH = 7.2 Hz, 6H, CH ₃ ), 1.16-1.36 (m, 12H, — (CH ₂ ) ₆ —) .
1,1,1,3,3,5,5-heptamine-5-octyl-trisiloxane (the above compound (VI))
¹ H NMR (400 MHz, CDCl ₃ ) δ = −0.13 (s, 6H, —Si (C H ₃ ) ₂ —), −0.13 (s, 6H, —Si (C H ₃ ) ₂ —) , 0.01 (s, 6H, —Si (C H ₃ ) ₂ —), 0.31 to 0.38 (m, 2H, SiC H ₂ ), 0.79 (t, J _HH = 7.2 Hz, _{_{3H, CH 2 C H 3)}} , 1.12-1.24 (m, 12H, (C H 2) 6).

[Example 20] Hydrosilylation reaction using ruthenium complex E A magnetic stirrer was added to a 20 mL Schlenk tube and heated and dried while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex E (24 mg, 0.03 mmol) was added to the Schlenk tube as a catalyst. 1-octene (112 mg, 1.0 mmol) was added thereto, and 1,1,1,3,3-pentamethyldisiloxane (163 mg, 1.1 mmol) was further added thereto, and then the solution was stirred at 80 ° C. for 23 hours. did. After cooling, anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 3 as entry 5.

[Example 21] Hydrosilylation reaction using ruthenium complex F A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex F (2.3 mg, 0.003 mmol) was added to the Schlenk tube as a catalyst. 1-octene (112 mg, 1.0 mmol) was added thereto, and 1,1,1,3,3-pentamethyldisiloxane (163 mg, 1.1 mmol) was further added thereto, and then the solution was stirred at 25 ° C. for 23 hours. did. After cooling, anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. These results are shown in Table 3 as entry 6.

(5) 1-octene hydrogenation using ruthenium complex

[Example 22] Hydrogenation reaction using ruthenium complex A A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex A (3.3 mg, 0.005 mmol) was added to the Schlenk tube as a catalyst, and dissolved in THF (2 mL). To this solution was added 1-octene (112 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 3 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 4 as entry 1.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.88 (t, J _HH = 7.2 Hz, 6H, CH ₃ ), 1.16-1.36 (m, 12H, — (CH ₂ ) ₆ —) .
¹³ C NMR (100 MHz, CDCl ₃ ) δ = 14.27, 22.86, 29.48, 32.10.

[Example 23] Hydrogenation reaction using ruthenium complex B A magnetic stirrer was added to a 20 mL Schlenk tube and dried while heating under reduced pressure to 5 Pa, and then the inside of the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex B (4.0 mg, 0.005 mmol) was added to the Schlenk tube as a catalyst, and dissolved in THF (2 mL). To this solution was added 1-octene (112 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 3 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 4 as entry 2.

[Example 24] Hydrogenation reaction using ruthenium complex C A magnetic stirrer was added to a 20 mL Schlenk tube and dried with heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (3.9 mg, 0.005 mmol) was added to the Schlenk tube as a catalyst and dissolved in THF (2 mL). To this solution was added 1-octene (112 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 3 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 4 as entry 3.

[Example 25] Hydrogenation reaction using ruthenium complex D After adding a magnetic stirrer to a 20 mL Schlenk tube and heating and drying while reducing the pressure to 5 Pa, the inside of the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex D (4.3 mg, 0.005 mmol) was added to the Schlenk tube as a catalyst, and dissolved in THF (2 mL). To this solution was added 1-octene (112 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 6 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 4 as entry 4.

[Example 26] Hydrogenation reaction using ruthenium complex F A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex F (3.8 mg, 0.005 mmol) was added to the Schlenk tube as a catalyst and dissolved in THF (2 mL). To this solution was added 1-octene (112 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 3 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 4 as entry 5.

(6) Hydrogenation of styrene using ruthenium complex

[Example 27] Hydrogenation reaction using ruthenium complex A A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex A (0.65 mg, 0.001 mmol) was added to the Schlenk tube as a catalyst, and dissolved in THF (2 mL). To this solution was added styrene (104 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 18 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 5 as entry 1.

^{_{1 H NMR (400MHz, CDCl 3}} ) δ = 1.13 (t, J HH = 7.2Hz, 3H, CH 2 C H 3), 2.54 (q, J HH = 7.2Hz, 2H, C H ₂ CH ₃ ), 7.02-7.11 (m, 3H, C ₆ H ₅ ), 7.11-7.20 (m, 2H, C ₆ H ₅ ).
¹³ C NMR (100 MHz, CDCl ₃ ) = 15.6, 28.8, 125.6, 127.8, 128.3, 144.3.

[Example 28] Hydrogenation reaction using ruthenium complex B A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex B (0.8 mg, 0.001 mmol) was added to the Schlenk tube as a catalyst, and dissolved in THF (2 mL). To this solution was added styrene (104 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 18 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 5 as entry 2.

[Example 29] Hydrogenation reaction using ruthenium complex C A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (0.77 mg, 0.001 mmol) was added to the Schlenk tube as a catalyst, and dissolved in toluene (2 mL). To this solution was added styrene (104 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 6 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 5 as entry 3.

[Example 30] Hydrogenation reaction using ruthenium complex D A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex D (0.86 mg, 0.001 mmol) was added as a catalyst to the Schlenk tube and dissolved in THF (2 mL). To this solution was added styrene (104 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 18 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 5 as entry 4.

[Example 31] Hydrogenation reaction using ruthenium complex E After adding a magnetic stirrer to a 20 mL Schlenk tube and heating and drying while reducing the pressure to 5 Pa, the inside of the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex E (2.44 mg, 0.003 mmol) was added to the Schlenk tube as a catalyst, and dissolved in THF (2 mL). To this solution was added styrene (104 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 1.5 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 5 as entry 5.

[Example 32] Hydrogenation reaction using ruthenium complex F A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex F (0.76 mg, 0.001 mmol) was added to the Schlenk tube as a catalyst, and dissolved in THF (2 mL). To this solution was added styrene (104 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 6 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 5 as entry 6.

(7) Hydrogenation of olefins using ruthenium complex C

[Example 33] Hydrogenation of methyl-10-undecenoate A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (3.9 mg, 0.005 mmol) was added to the Schlenk tube as a catalyst and dissolved in toluene (2 mL). To this solution was added methyl-10-undecenoate (198 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 1.5 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 6 as entry 1.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.88 (t, 3H, J _HH = 7.4 Hz, —CH ₃ ), 1.17-1.35 (m, 14H, —CH ₂ —), 1 .53-1.67 (m, 2H, —CH ₂ —), 2.30 (t, 2H, J _HH = 7.7 Hz, —CH ₂ C (═O) —), 3.66 (s, 3H , OMe).
¹³ C NMR (100 MHz, CDCl ₃ ) δ = 14.25, 22.83, 25.12, 29.31, 29.40, 29.45, 29.60, 29.70, 32.04, 34.28 , 51.57, 174.50.

[Example 34] Hydrogenation of cyclohexene A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (2.3 mg, 0.003 mmol) was added to the Schlenk tube as a catalyst and dissolved in toluene (2 mL). To this solution was added cyclohexene (82 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 4 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 6 as entry 2.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 1.43 (s, 12H, CH ₂ ).
¹³ C NMR (100 MHz, CDCl ₃ ) δ = 27.0.

[Example 35] Hydrogenation of ethyl-2,3-dimethyl acrylate A magnetic stirrer was added to a 20 mL Schlenk tube and dried under reduced pressure to 5 Pa, and then the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (2.3 mg, 0.003 mmol) was added to the Schlenk tube as a catalyst and dissolved in toluene (2 mL). To this solution, ethyl-2,3-dimethylacrylate (128 mg, 1.0 mmol) was added. The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 6 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 6 as entry 3.

^{_{1 H NMR (400MHz, CDCl 3}} ) δ = 0.93-0.96 (m, 6H, Me), 1.28 (t, 3H, OCH 2 C H 3), 2.00-2.04 (m , 1H, ChandCH ₂ C (═O)), 4.19 (q, 2H, OC H ₂ CH ₃ ).
¹³ C NMR (100 MHz, CDCl ₃ ) δ = 14.6, 22.9, 26.0, 43.6, 60.3, 173.5.

[Example 36] Hydrogenation of 2,3-dimethyl-2-butene A magnetic stirrer was added to a 20 mL Schlenk tube and dried under reduced pressure to 5 Pa, and then the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (3.9 mg, 0.005 mmol) was added to the Schlenk tube as a catalyst and dissolved in toluene (2 mL). To this solution was added 2,3-dimethyl-2-butene (84 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 6 hours. Anisole (108 mg, 1.0 mmol) was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 6 as entry 4.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.84 (d, J _HH = 6.7 Hz, 12 H, CH ₃ ), 1.40 (septet, J _HH = 6.7 Hz, 12 H, CH).
¹³ C NMR (100 MHz, CDCl ₃ ) δ = 19.4, 33.7.

[Example 37] Hydrogenation of trans-stilbene A magnetic stirrer was added to a 20 mL Schlenk tube and dried under reduced pressure to 5 Pa, and then the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (2.3 mg, 0.003 mmol) was added to the Schlenk tube as a catalyst and dissolved in toluene (2 mL). To this solution was added trans-stilbene (180 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 6 hours. Anisole was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 6 as entry 5.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 2.93 (s, 4H, CH ₂ ), 7.12-7.23 (m, 6H, C ₆ H ₅ ), 7.24-7.32 (m , 4H, C ₆ H ₅ ).
¹³ C NMR (100 MHz, CDCl ₃ ) δ = 37.9, 125.9, 128.3, 128.5, 141.8.

[Example 38] Hydrogenation of 1-methyl-1-cyclohexene A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (2.3 mg, 0.003 mmol) was added to the Schlenk tube as a catalyst and dissolved in toluene (2 mL). To this solution was added 1-methyl-1-cyclohexene (96 mg, 1.0 mmol). The resulting solution was freeze degassed and the inside of the Schlenk tube was replaced with a hydrogen atmosphere, and then the solution was stirred at room temperature for 3 hours. Anisole was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 6 as entry 6.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.86 (d, J _HH = 5.8 Hz, 3H, CH ₃ ), 1.04-1.28 (m, 4H, CH ₂ ), 1.28- 1.39 (m, 1H, CH) , 1.54-1.72 (m, 6H, CH 2).
¹³ C NMR (100 MHz, CDCl ₃ ) δ = 22.9, 26.3, 26.4, 32.7, 35.4.

[Example 39] Hydrogenation of (±) -limonene A magnetic stirrer was added to a 20 mL Schlenk tube and dried by heating while reducing the pressure to 5 Pa. Then, the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (7.7 mg, 0.010 mmol) was added to the Schlenk tube as a catalyst, and dissolved in toluene (2 mL). To this solution, (±) -limonene (136 mg, 1.0 mmol) was added. The resulting solution was transferred into an autoclave and the autoclave was replaced with hydrogen. Thereafter, the solution was stirred at room temperature for 6 hours under a hydrogen atmosphere of 10 atm. Anisole was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum (trans: cis = 1: 1). These results are shown in Table 6 as entry 7.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.847 (d, 2H, J _HH = 6.8 Hz, CH (CH ₃ ) ₂ of trans-isomer), 0.859 (d, 3H, J _HH = 6 .8 Hz, CH ₃ of trans-isomer), 0.860 (d, 2H, J _HH = 6.8 Hz, CH (CH ₃ ) ₂ of cis-isomer), 0.909 (d, 3H, J _HH = 6 8 Hz, CH ₃ of cis-isomer), 0.87-1.09 (m, 2H, CH and CH ₂ ), 1.18-1.58 (m, 6H, CH and CH ₂ ), 1.62 _{-1.77 (m, 3H, CH 2} ).
¹³ C NMR (100 MHz, CDCl ₃ ) δ = 19.5, 20.0, 20.4, 22.9, 25.5, 29.3, 29.7, 31.6, 33.0, 33.1 , 35.8, 43.2, 44.0.

[Example 40] Hydrogenation of diethyl isopropylidenemalonate A magnetic stirrer was added to a 20 mL Schlenk tube and dried under reduced pressure to 5 Pa, and then the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (7.7 mg, 0.010 mmol) was added to the Schlenk tube as a catalyst, and dissolved in toluene (2 mL). To this solution was added diethyl isopropylidenemalonate (200 mg, 1.0 mmol). The resulting solution was transferred into an autoclave and the autoclave was replaced with hydrogen. Thereafter, the solution was stirred at room temperature for 9 hours under a hydrogen atmosphere of 10 atm. Anisole was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 6 as entry 8.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.99 (d, J _HH = 6.3 Hz, 3H, CH ₃ ), 1.26 (t, J _HH = 7.3 Hz, 3H, CH ₃ ), 2 .38 (double of septet, J _HH = 6.3, 8.7 Hz, 1H, CHMe ₂ ), 3.10 (d, J _HH = 8.7 Hz, 1H, Me ₂ CH—CH—), 4.82 (Q, J _HH = 7.3 Hz, 2H, CH ₂ ).
¹³ C NMR (100 MHz, CDCl ₃ ) δ = 14.3, 20.5, 28.9, 59.3, 61.3, 169.0.

[Example 41] Hydrogenation of 2,3-dimethyl-1H-indene A magnetic stirrer was added to a 20 mL Schlenk tube and dried under reduced pressure to 5 Pa, and then the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (7.7 mg, 0.010 mmol) was added to the Schlenk tube as a catalyst, and dissolved in toluene (2 mL). To this solution was added 2,3-dimethyl-1H-indene (144 mg, 1.0 mmol). The resulting solution was transferred into an autoclave and the autoclave was replaced with hydrogen. Thereafter, the solution was stirred at 80 ° C. for 6 hours under a hydrogen atmosphere of 10 atm. Anisole was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 6 as entry 9.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 0.94 (d, 3H, J = 6.9 Hz, CH ₃ CHCH ₂ ), 1.14 (d, 3H, J = 7.2 Hz, CH ₃ CH), 2.49-2.61 (m, 2H), 2.94 (m, 1H), 3.17, (quintet, 1H, J = 6.9 Hz, CH ₃ CH), 7.06-7.24 ( _{_{m, 4H, C 6 H 4}} ).
¹³ C NMR (100 MHz, CDCl ₃ ) δ = 14.5, 15.0, 37.8, 39.2, 42.6, 123.5, 124.3, 126.0, 126.1, 142.8 , 149.0.

[Example 42] Hydrogenation of cinnamyl acetate A magnetic stirrer was added to a 20 mL Schlenk tube and dried under reduced pressure to 5 Pa, and then the inside of the Schlenk tube was replaced with an argon atmosphere. Ruthenium complex C (7.7 mg, 0.010 mmol) was added to the Schlenk tube as a catalyst, and dissolved in toluene (2 mL). To this solution was added cinnamyl acetate (176 mg, 1.0 mmol). The resulting solution was transferred into an autoclave and the autoclave was replaced with hydrogen. Thereafter, the solution was stirred at room temperature for 6 hours under a hydrogen atmosphere of 10 atm. Anisole was added as an internal standard, and the ¹ H-NMR spectrum was measured to determine the structure and yield of the product. The structure of the obtained compound was confirmed by ¹ H, ¹³ C-NMR spectrum. These results are shown in Table 6 as entry 10.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 1.96 (m, 2H, PhCH ₂ CH ₂ CH _2- ), 2.06 (s, 3H, Me), 2.70 (m, 2H, 2H, PhCH ₂ CH ₂ CH _2- ), 4.09 (t, 2H, J = 6.8 Hz, PhCH ₂ CH ₂ CH _2- ), 7.17-7.23 (m, 3H, Ph), 7.27- 7.32 (m, 2H, Ph).
¹³ C NMR (100 MHz, CDCl ₃ ) δ = 21.1, 30.3, 32.3, 64.0, 126.2, 128.5, 128.6, 141.3, 171.3.

(8) Reduction of N, N-dimethylformamide using ruthenium complex

[Example 43] Reaction using ruthenium complex C After drying the NMR tube under reduced pressure to 5 Pa, ruthenium complex C (39 mg, 0.05 mmol) was added as a catalyst, and 0.4 mL of heavy benzene was added by syringe. . Thereafter, dimethylphenylsilane (600 mg, 4.4 mmol) was added, and N, N-dimethylformamide (73 mg, 1.0 mmol, hereinafter referred to as DMF) was added, and then the NMR tube was burned off under vacuum and sealed in a vacuum. After the solution was stirred at 120 ° C. for 5 hours, formation of amine was confirmed by ¹ H-NMR spectrum. These results are shown in Table 7 as entry 1.

¹ H NMR (400 MHz, CDCl ₃ ) δ = 2.12 (s, 9H, NMe ₂ ).

[Example 44] Reaction using ruthenium complex E After heating and drying the NMR tube at 5 Pa under reduced pressure, ruthenium complex E (4.1 mg, 0.005 mmol) was added as a catalyst, and 0.4 mL of heavy benzene was added with a syringe. added. Thereafter, dimethylphenylsilane (600 mg, 4.4 mmol) was added, and DMF (73 mg, 1.0 mmol) was further added, and then the NMR tube was burned off under reduced pressure and vacuum sealed. After the solution was stirred at 120 ° C. for 5 hours, formation of amine was confirmed by ¹ H-NMR spectrum. These results are shown in Table 7 as entry 2.

[Example 45] Reaction using ruthenium complex F After drying the NMR tube under reduced pressure to 5 Pa, ruthenium complex F (38 mg, 0.05 mmol) was added as a catalyst, and 0.4 mL of heavy benzene was added by syringe. . Thereafter, dimethylphenylsilane (600 mg, 4.4 mmol) was added, and DMF (73 mg, 1.0 mmol) was further added, and then the NMR tube was burned off under reduced pressure and vacuum sealed. After the solution was stirred at 120 ° C. for 5 hours, formation of amine was confirmed by ¹ H-NMR spectrum. These results are shown in Table 7 as entry 3.

Claims

A neutral or cationic mononuclear ruthenium divalent complex represented by the formula (1):

(Wherein R 1 to R 6 are independently of each other a hydrogen atom, X may be substituted with alkyl group, aryl group, aralkyl group, organooxy group, monoorganoamino group, diorganoamino group. Represents a monoorganophosphino group, a diorganophosphino group, a monoorganosilyl group, a diorganosilyl group, a triorganosilyl group, or an organothio group, or any of R 1 to R 3 and any of R 4 to R 6 A bridged substituent in which at least one pair of
X represents a halogen atom, an organooxy group, a monoorganoamino group, a diorganoamino group, or an organothio group,
L represents a two-electron ligand other than CO and a thiourea ligand independently of each other, and two L may be bonded to each other;
m represents an integer of 3 or 4. )
L is molecular hydrogen, amine, imine, nitrogen-containing heterocycle, phosphine, phosphite, arsine, alcohol, thiol, ether, sulfide, nitrile, isonitrile, aldehyde, ketone, alkene having 2 to 30 carbon atoms, carbon number The neutral or cationic mononuclear ruthenium divalent complex according to claim 1, which is at least one dielectron ligand selected from 2 to 30 alkynes and triorganohydrosilane.
The neutral or cationic mononuclear ruthenium bivalent complex of Claim 1 represented by Formula (2).

(Wherein R 1 to R 6 represent the same meaning as described above).
L 1 represents at least one dielectron ligand selected from isonitrile, amine, imine, nitrogen-containing heterocycle, phosphine, phosphite and sulfide. When a plurality of L 1 are present, two L 1 are May be joined together,
L 2 represents CO, a thiourea ligand, and a two-electron ligand other than L 1. When a plurality of L 2 are present, two L 2 may be bonded to each other,
m 1 represents an integer of 1 to 4, m 2 represents an integer of 0 to 3, and m 1 + m 2 satisfies 3 or 4. )
L 1 represents at least one dielectron ligand selected from isonitrile, nitrogen-containing heterocycle and phosphite (provided that when a plurality of L 1 are present, two L 1 are bonded to each other). The neutral or cationic mononuclear ruthenium divalent complex according to claim 3.
Wherein L 2 is a tri-organo-hydrosilane (when L 2 there are a plurality, two L 2 may also be bonded to each other) according to claim 3 or 4, wherein a neutral or cationic mononuclear ruthenium Bivalent complex.
The neutral or cationic mononuclear ruthenium divalent complex according to any one of claims 3 to 5, wherein both m 1 and m 2 are 2.
R 1 to R 6 are each independently an alkyl group, aryl group or aralkyl group (X represents the same meaning as described above), which may be substituted with X, and
L 2 is H-SiR 7 R 8 R 9 and H-SiR 10 R 11 R 12 (wherein R 7 to R 12 are each independently an alkyl group optionally substituted with X, Represents an aryl group or an aralkyl group, and X represents the same meaning as described above.)
Any one of R 1 to R 3 and at least one set of any of R 4 to R 6 or at least one set of any of R 7 to R 9 , or any of R 10 to R 12 ; At least one set of any of R 4 to R 6 or at least one set of any of R 7 to R 9 may be combined to form a bridging substituent,
Any one of R 1 to R 3 and at least one set of any of R 4 to R 6 or at least one set of any of R 7 to R 9 together form a bridging substituent, and R 10 Any one of -R 12 may be combined with at least one set of any of R 4 -R 6 and at least one set of any of R 7 -R 9 together to form a bridging substituent. Neutral or cationic mononuclear ruthenium divalent complex as described.
The neutral or any one of claims 1 to 7, wherein any one of R 1 to R 3 and any one of R 4 to R 6 are combined together to form a bridging substituent. Cationic mononuclear ruthenium divalent complex.
Any one of R 1 to R 3 and any one of R 4 to R 6 or any one of R 7 to R 9 together form a bridging substituent, and R 10 to Any one of R 12 and any one of R 4 to R 6 and any one of R 7 to R 9 together with a substituent on Si that is not involved in the formation of the bridging substituent; The neutral or cationic mononuclear ruthenium divalent complex according to claim 7, which forms a crosslinking substituent.
Any one of R 1 to R 3 and any one of R 4 to R 6 together form an o-phenylene group which may be substituted with Y (Y is a hydrogen atom, a halogen atom, An atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and when there are a plurality of Y, they may be the same or different from each other), and any of R 10 to R 12 And any one of R 7 to R 9 together form an o-phenylene group optionally substituted with Y (Y is as defined above). Neutral or cationic mononuclear ruthenium divalent complex as described.
A catalyst having activity in at least one reaction selected from a hydrosilylation reaction, a hydrogenation reaction, and a reduction reaction of a carbonyl compound, comprising a neutral or cationic mononuclear ruthenium divalent complex according to any one of claims 1 to 10. .
12. A process for producing an addition compound, comprising subjecting a compound having an aliphatic unsaturated bond and a hydrosilane or organohydropolysiloxane having a Si—H bond to a hydrosilylation reaction in the presence of the catalyst according to claim 11.
A method for producing an alkane compound, comprising hydrogenating a compound having an aliphatic unsaturated bond in the presence of the catalyst according to claim 11.
A method for producing an amine compound, comprising reducing an amide compound with a silane or an organohydropolysiloxane having a Si-H bond in the presence of the catalyst according to claim 11.
12. A method for producing an alcohol compound, comprising reducing an aldehyde compound, a ketone compound or an ester compound with a silane or organohydropolysiloxane having a Si—H bond in the presence of the catalyst according to claim 11.